Phosphate salts of amine based polyols

ABSTRACT

Disclosed is the phosphate salt of amine based polyols which are useful in preparing low density polyurethane foams. The phosphate salt of amine based polyols includes those compositions prepared by reacting alkoxylated mono- and/or polyamines with phosphoric acid. Rigid low density polyurethane foams are prepared from a polyol blend of a phosphate salt of an amine based polyol and one or more other polyhydroxy compounds.

United States Patent [191 Fowler June 17, 1975 PHOSPHATE SALTS OF AMlNEBASED POLYOLS [75] Inventor: Raymond ll. Fowler. Chadds Ford,

[73] Assignee: lCl United States Inc., Wilmington,

Del.

[22] Filed: Feb. 23, 1973 [21] Appl. No.: 335,369

[52] US. Cl.. 260/584 B; 260/2.5 AQ; 260/2.5 AR;

260/584 R [51] Int. Cl. C07c 91/02 [58] Field of Search 260/584 B, 584 R[56] 8 References Cited UNlTED STATES PATENTS 4/1962 Moseley ct al260/584 B 6/l962 Seidel et al 260/584 B 3,438,986 4/l969 Kaiser et al.260/584 B 3,578,607 5/1971 Riggs et al 260/584 B FOREIGN PATENTS ORAPPLICATIONS 1,130,512 [1/1965 United Kingdom 260/584 B PrimaryExaminerElbert L. Roberts Assistant Examiner-D. R. Phillips 5 7 ABSTRACT7 Claims, No Drawings PHOSPHATE SALTS OF AMINE BASED POLYOLS Thisinvention relates to the phosphate salt of amine based polyols and tolow density cellular polyurethanes made therefrom.

Rigid polyurethane foams have found extensive use in modern industrialapplications with respect both to the structural and to the insulativecapacities thereof. Rigid low density polyurethane foams have in thepast frequently exhibited disadvantageous characteristics of markedthermal instability, as evidenced by their tendency to shrink in volumeat reduced temperatures or even at ordinary temperatures. Such shrinkageis usually attributable to the collapse, upon condensation to a liquidof the gaseous foaming agent, of relatively attenuated, and consequentlyweak, cell walls of the foam which result from the high ratio of suchfoaming agent to polyurethane materials employed in the foam formulationin order to produce a foam of low density.

It is an object of the present invention to provide novel phosphatesalts of amine based polyols which can be used to prepare rigid lowdensity polyurethane foams which are stable at low temperatures.

It is the further object of the present invention to provide rigid lowdensity, thermally stable cellular polyurethanes.

It is another object of the present invention to provide rigid lowdensity polyurethane compositions which exhibit excellent freezerstability while retaining the insulation value, and other desirablephysical property characteristics of rigid polyurethane foams.

These and other objects are achieved in accordance with the presentinvention through the use of a phosphate salt of an amine based polyol apolyol component in the preparation of polyurethane foams.

The phosphate salts of amine based polyols of the present invention areprepared by adding sufficient phosphoric acid to the amine based polyolso as to result in the formation of either a partially neutralized orcompletely neutralized amine based polyol.

The amine based polyols or polyoxyalkylene amines which are used asprecursors in the preparation of the present phosphate salts of aminebased polyols can be prepared from any of the well-known commerciallyavailable monoand polyamines. In general, such amines containing fromabout 1 to carbon atoms can be used in accordance with the presentinvention; however, in a preferred embodiment of this invention, suchamines containing 2 to 6 carbon atoms are utilized. Among the polyaminesthat can be used are any of the known diamines, triamines, andtetramines. These amines, in turn, are reacted with an alkylene oxide toform polyoxyalkylene amines also known as polyethers.

The polyoxyalkylene amines which are used to make the amine based polyolphosphates of the present invention will generally have a hydroxylnumber between about 350 and 800 and wwll contain from 3 to 30 mols ofalkylene oxide per mol of amine. However, in a more preferred embodimentthe polyol amines which are used to prepare the subject polyol aminephosphates will contain from about 3 to mols of alkylene oxide per molof amine. The alkylene oxide used can contain from 2 to 6 carbon atomsbut is preferably propylene oxide or mixtures of ethylene oxide andpropylene oxide.

In another preferred embodiment of the present invention the lowernumber of mols of alkylene oxide used to prepare the subjectpolyoxyalkylene amines should be that number which is sufficient toreact with each amino hydrogen present in the amine and an upper limitof about 20 mols of alkylene oxide per mol of amine.

In more preferred embodiments of the present invention, the polyol aminephosphates of the present invention based on a diamine will contain from4 to 8 mols of alkylene oxide per mol of diamine. Those amine polyolphosphates of the present invention based on monoamines will containfrom 3 to 8 mols of alkylene oxide per mol of monoamine. Preferred aminepolyol phosphates of the present invention based on triamines willcontain from 5 to 9 mols of alkylene oxide per mol of amine, whereas thepolyol phosphate amines of the present invention based on tetramineswill contain from 6 to 10 mols of alkylene oxide per mol of tetramine.

In the above discussion of polyoxyalkylene amines and theircorresponding phosphates, it is understood that when it is stated that apolyol amine or polyol amine phosphate'contains a certain number" ofmols of alkylene oxide per mol of amine, it is meant that the amine issuitably reacted with said certain number or mols of alkylene oxide andthus the resulting polyether or polyoxyalkylene amine will actuallycontain groups or residues of the alkylene oxide used corresponding tothe certain number of mols of alkylene oxide used to prepare thepolyoxyalkylene amine.

In accordance with the present invention, the subject phosphate salts ofaliphatic amine based polyols can be prepared by reactingpolyoxyalkylene amines, as described above, with from about 0.25% toabout 10% by weight of concentrated phosphoric acid (86%), based on thetotal weight of polyoxyalkylene aminephosphoric acid reaction mixture,to form the phosphate salt thereof. In a more preferred embodiment fromabout 0.50 to about 5.00% by weight of concentrated phosphoric acid(86%), based on the total weight of polyoxyalkylene amine-phosphoricacid reaction mixture, is reacted with the above describedpolyoxyalkylene amines to prepare the subject phosphate salts of aminebased polyols. It will be understood by those skilled in the present artthat the desired concentration of phosphoric acid as indicated above canbe obtained through the use of a different strength acid (other than86%). The preparation of such phosphate salts is accomplished by meremixing of the polyoxyalkylene amine and phosphoric acid so as to bringabout a thorough and intimate contact between the two reactants for thepurpose of reaction at temperatures from about room temperature (F.) upto about l50F. for about 5 to 30 minutes.

Some of the preferred novel phosphate salts of aliphatic amine basedpolyols (polyethers) of the present invention can be represented by thefollowing general formulas:

wherein R is selected from the group consisting of alkylene groupscontaining from 1 to 20 carbon atoms,

*3 R-N- R- and R is independently selected from the group consisting ofalkylene groups containing from 1 to 6 carbon atoms, Q is independentlyselected from the group consisting of hydrogen and (OR'),,H, R isindependently selected from the group consisting of alkylene groupscontaining from 2 to 6 carbon atoms, v is a number of from 1 to 20, x isa number of from 1 to 20, z represents a number having an average valueof 3 and m and p are independently selected values ofO or I with theproviso that at least m or p is l, n has a value of from 0.03 to 0.5, thas a value of 0.03 to 1.0 when the amine represented by formula (b) isa diamine, and a value of 0.05 to 1.5 and 0.05 to 2.0 when the aminerepresented by formula (b) is a triamine and tetramine, respectively.

In a more preferred embodiment of the present inven- 7 tion, 11 has avalue of about 0.05 to 0.5, t has a value of about 0.05 to 1 when theamine represented by formula (b) is a diamine, and y and .rindependently represent numbers from 1 to 15. In the above formula n andI represent the number of mols of H PO that are reacted with l mol ofpolyoxyalkylene amine.

Polyurethane foams of the present invention are made from polyolcompositions containing from about 5 to about 100%, more preferably 10to 40% and most preferably 20 to 40% by weight, of the amine basedpolyol phosphates of the present invention as described above. The otherportion of the polyol blend that can be used in the preparation of thesubject low density foams can be made up of any of the suitablecommercially available hydroxyl-bearing compounds having terminalhydroxyl groups which are thoroughly described throughout the prior artand hereinafter. In a preferred embodiment the polyol compositions ofthe present invention which can consist solely of the abovedescribedamine based polyol phosphates or a blend of such phosphates with asecond polyol or polyhydric alcohol, having a hydroxyl functionality ofthree or more, will have a hydroxyl number within the range of 350 to650, preferably 400 to 500.

polyethers) which are used as precursors in the preparation of the novelphosphate salts of amine based polyols (polyolamine phosphates) of thepresent invention are well known in the art, inasmuch as they have beenextensively used as polyols in the preparation of polyurethanes, andthey can be prepared by known processes. For example, suchnitrogen-containing polyethcrs can be prepared from any of thecommercially available aliphatic amines containing from 1 to 10 carbonatoms, such as monoethanolamine, tricthanolamine, ethylenediamine,triethylenetetramine, diethyl enetriamine, hexamethylenediaminc,istmropylamine. 1,o-hexamethylenediamine. hexylamine, and butylamine, byreacting such amines with a lz2-alkylene oxide. In most instances. thealkylene oxide used is ethylene oxide or propylene oxide or acombination thereof; however, such alkylene oxides containing up to sixcarbon atoms can be used. The method of preparing suchnitrogen-eontaining polyethers as stated above is welltrimethylolethane,

known in the art. for example, as disclosed in US. Pat. No. 3,094,434and in standard texts such as Saunders et al., "Polyurethanes: Chemistryand Technology," Part I and Part ll, lnterscience Publishers, New York,1962 and l964, respectively. Further, polyoxyalkylene amine precursorsused to prepare the novel phosphate salts of amine based polyols arecommercially available.

Among the polyoxyalkylene amines which are suitable for use in thepreparation of the phosphate salt amine based polyols of the presentinvention are: polyoxyethylene(8) ethylenediamine; polyoxypropylenel2)triethylenetetramine; polyoxypropylene( 3 )polyoxyethylene( l)ethylenediamine; polyoxyethylene( 3 )polyoxypropylene( 2)diethylenetriamine'. polyoxypropylene(2)ethanolamine;polyoxypropylene(3)diethanolamine; polyoxypropylene(8)tricthanolamine;polyoxyethylene(6)-l ,4-butanediamine; polyoxypropylene(S )-1,5-pentanediamine; polyoxypropylene (5 )ethylenediamine;polyoxypropylcne(2)-polyoxyethylene(2)ethylenediamine; and mixturesthereof.

The polyurethane compositions falling within the ambit of the presentinvention are broadly those cellular compositions comprising multipleurethane linkages formed by the reaction of an isocyanate and a compoundcontaining a hydrogen atom or atoms reactive therewith, as, for example,hydroxyl-bearing compounds having terminal hydroxyl groups such aspolyesters and polyethers. Polyhydric compounds which are blended withthe novel phosphate salt amine based polyols of the present invention toprepare polyurethane foam compositions of the present invention comprisethose having a hydroxyl functionality of three or more. In general,polyhydric compounds, i.e., polyethers and polyesters, having from threeto nine hydroxyl groups in the molecule thereof are used to prepare thepolyurethane foams of the present invention. These may be. for example,triols. tctrols, pentitols. hexitols, heptitols, octitols, nonitols, andmixtures thereof in any proportion. ln accordance with this invention,however, such polyhydrie compounds will generally have a hydroxyl numberbetween about 350 and 650 inclusive.

The term hydroxyl number as used throughout this specification denotesthe number .of milligrams of potassium hydroxide equivalent to the acidrequired to estcrify 1 gram of the hydroxylic material; the equivalentweight of the hydroxylic material, therefore, is the weight in gramsthereof which contains one gram mol 5( of the hydroxyl radical, i.e.,56,100 divided by hydroxyl The polyoxyalkylcnc amines(nitrogen-containing number.

Polyether hydroxylic compounds which may be used in combination with thesubject phosphate salts of aliphatic amine based polyols to preparepolyurethane foam compositions in accordance with this inventioncomprise polyoxyalkylcne ethers of polyhydric alcohols, such aspolyoxyalkylene triols, tctrols, pentitols, hexitols, and polycthers ofstill higher functionality. Such polyethers are exemplified bypolyoxyalkylene polyoxyalkylene trimethylolpropane, polyoxyalkylenehexanetriol, polyoxyalkylene glycerol. polyoxyalkylene butanetriol,polyoxyalkylene erythritol. polyoxyalkylene pentaerythritol,polyoxyalkylene sorbitol, polyoxyalkylene methyl glucoside,

polyoxyalkylene sucrose, polyoxyalkylene mannitol,

More specifically, among'the hydroxyl-bearing compounds which maysuitably be used in combination with the novel phosphate salts ofaliphatic amine based polyolsto prepare polyurethane foams in accordancewith this invention are: polyoxypropylene( l) sorbitol,polyoxypropylcne( 4 )hexanetriol, polyoxybutylene( 8) glycerol,polyoxypropylene 5 )mannitol, propylene( 3 )trimethylolethane,polyoxypropylene( 8 trimethylolpropane', polyoxypropylene (4)sorbitol,polyoxybutylene( )lactositol, polyoxyethylene( 6- )methyl glucoside,polyoxypropylene( l2 )sorbitan, polyoxypropylene(8 )erythritol,polyoxybutylene(4)pentaerythritol, polyoxyethylene( 3 )polyoxypropylene(7- )mannitan, polyoxyethylene (4)polyoxypropylene(10- )sucrose andmixtures thereof and many others. Generally,'such polyethers willcontain from 3 to 20 mols (residues) of alkylene'oxide per mol ofpolyhydric alcohol.

Since the hydroxyl number of the polyol is a function of the number. ofhydroxyl groups per molecule thereof and the molecular weight of thecompounds, it will be evident that the overall range of oxyalkylation inthe polyol used inaccordance with this invention is limited by thepreviously defined permissible range in hydroxyl number thereof.

Polyesters suitable for use in the preparation of polyurethane foams ofthis invention may be obtained by esterification condensation reactionof an aliphatic di basic carboxylic acid with a trio] or an alcohol ofhigher hydroxylic functionality, or mixtures thereof, in such proportionthat the resultant polyesters possess predominately terminal hydroxylgroups.

Polyhydroxylic compounds suitable to the preparation of such polyestersare exemplified by glycerol, 1,2- hexanetritol, trimethylolethane,trimethylolpropane, sorbitol, m'ethyl 'glucoside, lactositol, mannitol,and, in general; any similar polyhydric compound which when reacted insuitable proportion with a dibasic acid will provide a polyester with ahydroxylic functionality within the range of three to nine.

Aliphatic diearboxylic acids which may be used to prepare such,polyesters comprise adipic acid, fumaric acid, sebacic acid, phthalicacid, maleic acid, and many other acids of the kind.

Methods of preparation of polyesters suitable for use in the preparationof polyurethane foams are abundantly described in U .S. Pat. Nos.2,543,644; 2,593,787; 2,409,633; 2,443,735; 2,443,741; 2,450,552;2,255,313; 2,512,410; 2,634,251;

2,662,069; and 2,662,070 all hereby incorporated by reference.v

.A wide variety of organic isocyanate compounds may be used to preparethe novel polyurethane foam compositions of the present invention amongwhich are ineluded toluene diisoeyanate (both the 2,4- and 2,6- isomersand any mixture thereof), biphenyl diisocyanate, terphenyl diisocyanate,chloro-phenylene-l,4- diisocyanate, l,4-tetramethylene diis'oeyanate,pphenylene diisocyanatc, polymethylene polyphenyl isocyanate (PAPI),3;.3'-dimethoxy-4.4'-biphenylene diisocyanate, diphen vlmethane,4,4'-diisocyanat e, and

others.

Catalysts which may be used in the preparation of polyurethane foams ofthe present invention may include well-known amine catalysts which havebeen used to catalyze such reactions in the prior art. Among thesuitable amine catalysts are dimethylethanolamine,

polyoxy 6 N-methyldicyclohexylamine, and N,N-dimethyleyclohexylamine.These amine catalysts are generally used in amounts from about 0.05 toabout 2% by weight of the hydroxyl-bearing compounds reacted with theisocyanate compound. In instances where the amine based polyol phosphatecompounds of the present invention contain excess or unreactedphosphoric acid (not reacted with the amine based polyol reactant).additional quantities of amine catalyst may be used so as to neutralizethe excess phosphoric acid and provide a catalytic concentration of theamine catalyst to catalyze the isocyanatepolyol reaction.

Examples of useful surface active agents which can be present in amountsof from about 0.05 to about 27: by weight of the hydroxyl-bearingcomponents used to prepare the polyurethane foams are water-solublesiloxane-oxyalkylene block copolymers as described in US, Pat. No.2,834,748 to Bailey et al., issued May 13. 1958. Other surfactants whichmay be used are condensates of ethylene oxide with a hydrophobic baseformed by condensing propylene oxide with a propylene glycol. Thesesurfactants have a molecular weight within the range of about 2000 toabout 8000 and are generally ascribed the formula:

lllustrative examples of foaming agents which may be used in thepreparation of polyurethane foams of the present invention includewater, a halogenated saturated aliphatic hydrocarbon or a mixture ofsuch halogenated saturated aliphatic hydrocarbons; for example,trichlorofluoromethane (Freon 1 l monochloroethane;monochloromonofluoroethane;\ 1,2-dibromo- 1,1 ,2,2-tetrafluoroethane;1,1,2-trifluoroethane; 1,1,2- ,2-tetrafluoro-1,2-dichloroethane;l,2-difluor0-1,1,2,2- tetrachloroethane; dichloromethane;dibromomethane, and their mixtures. A mixture of a halogenated saturatedaliphatic hydrocarbon and water is a preferred foaming agent. Inaccordance with the method of this invention, not less than about 10% byweight nor more than about 25% by weight based on the total foamformulation of a suitable foaming agent, such as any of those set forthabove or other similar foaming agents, is used to prepare the lowdensity foam compositions included within the purview of this invention.

Within the context of this specification, the term low density, whenused with reference to the cellular polyurethane compositions of thisinvention, denotes foams having a density within the range of about 0.75pound per cubic foot to about 1.7 pounds per cubic foot. Preferably, thefoams of the present invention have a density lying within a range ofabout 1.2 pounds per cubic foot to about 1.5 pounds per cubic foot.Polyurethane foams having a density greater than 1.7 pounds per cubicfoot are not deemed to be foams of low density within the meaning ofthat term as used herein.

The polyurethane foams provided in accordance with this invention arerigid foams as distinguished from flexible or semi-rigid foams.Throughout this specification the term rigid," when used with referencesto the polyurethane foams of this invention, denotes foams having lessthan about 20% volume recovery when compressed by about l07( of thevolume thereof. Rigid foams of this invention, moreover, comprise foamshaving not less than about of the cells thereof in the form of closedcells. If more than about 25% of the cells of the said foams were opencells. the insulation values of the foams would be unsatisfactory.

The cellular polyurethane compositions of this invention may be preparedin the conventional manner thoroughly described in the prior art bymixing a polyhydroxylic blend, as hereinbefore described, with apolyisocyanate compound, as hereinbefore specified, in approximatelystoichiometrie proportion, based upon the hydroxyl number of thepolyhydric component. In general, polyurethane foams of the presentinvention are prepared by reacting a hydroxyl-bearing component with anorganic isocyanate in suitable proportion to provide a ratioofisocyanate groups to hydroxyl groups with a range of about 0.9 toabout 1.25 with a preferred range for said ratio from about 1.0 to about1.1. The polyol component and the isocyanate component are mixedvigorously to promote reaction and thereafter the reaction mixture ispoured and allowed to foam to completion.

The following examples are illustrative of compositions which are usefulas'the polyol component for preparing the polyurethane compositions ofthis invention. These examples are set forth solely for the purposes ofillustration and any specific enumeration of details contained thereinshould not be interpreted as expressing limitations of this invention.It will be readily apparent to those skilled in the art that othercompositions may be prepared by substituting other polyols,polyisocyanates, catalysts, surfactants, and blowing agents for thoserecited in the following examples. All percentages are by weight.

EXAMPLE 1 172.4 Pounds of molten sorbitol containing less than 0.2%water were mixed with 480 grams of powdered sodium hydroxide and placedin an autoclave. The autoclave was sealed, flushed 3 times at psig withnitrogen gas. heated to 165C., and then a vacuum was drawn on theautoclave down to about 50 millimeters of mercury pressure. Propyleneoxide (477.6 pounds) was added at 165C./85 psig to the autoclave and thecontents of the autoclave pumped through a heat exchanger to maintainthe temperature and cause mixing of the mixture until the pressure wassubstantially zero. The mixture was then deodorized by vacuum strippingminutes at 120C. The resulting polyol was then diluted with an equalamount of distilled water and the diluted mixture was passed through acation and anion exchange column and then vacuum stripped at 120C. for 1hour to yield the desired polyol containing less than 0.1% water. Theresulting polyoxypropylene sorbitol product had a hydroxyl number of420, viscosity of 18,600 centipoises at C., and a water content of0.09%.

EXAMPLE 2 Ethylenediamine (40 pounds) containing 0.25% water was placedin an autoclave and flushed three times with nitrogen gas and thenheated to 120C. by circulation through a heat exchanger. Then 60 poundsof propylene oxide were added at a rate to keep the temperature andpressure within the autoclave at about 135C./25 psig. The mixture in theautoclave was agitated and 96.6 pounds more propylene oxide were addedat a rate to keep temperature and pressure at about 135C./25 psig. Thereaction mixture in the autoclave was heated for about three hours atabout 135C.

initially at a pressure of about 25 psig, until the pres sure dropped tosubstantially zero. The reaction mixture was then cooled to 100C. 74Grams of powdered sodium hydroxide were added to the reaction mixture inthe autoclave under a nitrogen gas flow, and then the autoclave washeated to 155C./55 psig. Then a vacuum of about 50 millimeters ofmercury was drawn and 130.3 pounds of propylene oxide were added at arate to maintain temperature and pressure at about 155C./55 psig, whilethe reaction mixture was circulated through a heat exchanger until asubstantially zero pressure was obtained. The resulting polyoxypropyleneethylenediamine polyol was then deodorized by vacuum stripping 15minutes at 120C. under a vacuum of about 50 millimeters of mercurypressure. Then, to deash the polyol product, 1.6% sodium acidpyrophosphate and 5% distilled water were added to the resulting polyol.This blend was then agitated for two hours and then stripped at 1 10C.at a final vacuum of about 50 millimeters of mercury pressure to a watercontent of less than 0.08%. Then 0.2% magnesium silicate and 0.4% SuperCel were added to the polyol. The resulting mixture was then filteredand the resulting 'polyoxypropylene ethylenediamine polyol product had ahydroxyl number of 464 and a water content of 0.06%.

EXAMPLE 3 36.9 Pounds of polyoxyethylene(4)-ethylenediamine were treatedwith 14 grams of powdered sodium hydroxide catalyst and 27.7 pounds ofpropylene oxide by the process of Examples 1 to yield apolyoxyethylene(4) polyoxypropylene-ethylenediamine polyol. This productwas deashed by the following procedure. 39.2 Grams of phosphoric acidand 54.5 grams of water were added to the above polyol product andheated at a temperature of C. for 2 hours with agitation. The productwas then vacuum stripped at 1 10C. to yield a polyol containing 0.08%water. 54.5 Grams of magnesium silicate were then added to the polyoland the mixture was filtered to yield a polyoxyethylene polyoxypropyleneethylenediamine polyol having an acid number of 0.50. and a hydroxylnumber of 443. The polyol product had a viscosity of 4,520 centipoisesat 25C.

EXAMPLE 4 EXAMPLE 5 By the method of Example 1. 80 pounds of moltensorbitol. 240 grams of powdered sodium hydroxide. and 245 pounds ofpropylene oxide were charged to an autoclave and reacted to form apolyoxypropylene sorbitol polyol. The polyol obtained was then deashedby the method of Example 2. The resulting product had a hydroxyl numberof 440. water content of 0.07%, and

an acid number of 0.15. The polyol product had a viscosity of 22.300centipoises at 25C.

EXAMPLE 6 4.8 Pounds monoethanolamine were charged into an autoclave and1 1.2 pounds of sucrose were slowly added and mixed into themonoethanolamine. Then 109 grams of powdered sodium hydroxide werestirred into the above mixture and the autoclave was sealed and flushedthree times at psig with nitrogen. A nitrogen blanket was then appliedat atmospheric pressure and the reaction was heated to 110C. Then 54pounds of propylene oxide were slowly added to the autoclave at a rateso to maintain the temperature at about 1 10 to l C./40 to 50 psig. Thereaction mixture was maintained at this temperature and stirred untilthe pressure was substantially zero for 30 minutes. The resultingproduct was then deodorized by vacuum stripping for 15 minutes at about120C. When the temperature of the product was about 105C., 0.988% byweight of phosphoric acid (85%) was added to the reaction mixture whichwas then stirred for about 30 minutes. The resulting mixture was thenvacuum stripped at about 1 10C. under vacuum of about 50 millimeters ofmercury until the water content was less than 0.05%. 0.1% Dalpac C-4 wasthen added to the resulting polyol product and thoroughly agitatedtherein and then the resulting product was filtered through paper toyield a polyol blend consisting of polyoxypropylene monoethanolamine andpolyoxypropylene sucrose having a hydroxyl number of 408, water contentof 0.18%, and acid number of 2.00. The polyol product had a viscosity of4,030 centipoises at 25C.

1n the following Examples 8, 9. 11, 12, 14. and 15. polyurethane foamswere prepared using novel phos phate salt amine based polyols of thepresent invention. Examples 7 and 10 are controls for Examples 8, 9. l1, and 12, and Example 13 is the control for Examples 14 and 15. Thefoams of Examples 7 to 15 were prepared using the following hand-mixingprocedure.

Hand-Mixing Procedure The polyols were weighed into a 12-ounce uncoatedpaper cup. Those polyols having phosphoric acid added thereto to preparethe novel phosphate salts of the amine based polyols were first heatedto about 120F. along with the added phosphoric acid under mechanicalagitation for about minutes in order to effect the preparation of thedesired phosphate salts of the amine based polyols. Chemical analysisconfirmed the formation ofthe said phosphate salts of the amine basedpolyols. The other B component ingredients were then added in the orderlisted from top to bottom, each being weighed into the cup until all theingredients were added except the isocyanate. These were then mixed witha conventional laboratory electric stirrer at approximately 1,500 rpmuntil homogenous. The weight was then rechecked and any halogenatedhydrocarbon blowing agent loss was made up by adding back the weightlost. This mixture constitutes what is referred to as B component in thelisting of ingredients under each example. The isocyanate (referred toas the A component) is then added rapidly to the cup (B component) andthe total loam ingredients were mixed for 10 seconds with the previouslymentioned mixer. The resulting mixture is then poured rapidly into amold. The mold utilized was a metal mold. 2 by 7 by l2 [Weight PackedFoam Panel Minus Weight Free Blown Foam PanellX Weight Free Blown FoamPanel Percent Packing The percent freezer shrinkage of the products ofthe following Examples 7 to 15 were determined by measuring theshrinkage of the molded polyurethane foam in the 7-inch direction afterexposure of the foam to 20F. temperature for 16 hours. For mostcommercial uses it is preferred that free blown foam panels should havea shrinkage less than 10% under the above-stated testing procedure;whereas packed foam panels should have a shrinkage below 3% under thesame test conditions. However, free blown foam panels which exhibit ashrinkage less than 20% and packed foam panels exhibiting a shrinkageless than 15% under the abovestated testing procedure are also withinthe bounds of the present invention inasmuch as such products can beutilized in areas and uses when the thermal conditions are not quite sosevere.

EXAMPLE 7 Component A Percent by Weight Nacconate 5050 (eommericaltolylene diisocyanate containing a mixture of 8071 2,4- and 2071 2.6-isomers).

Component B 44.26 Percent by Weight Polyol of Example 1 25.00 Polyol ofExample 3 6.74

( I )-ethylene oxide-( 3 )-propylene oxide ethylene diamine 3.95Organo-silicone surfactant L-5340 (Union Carbide Co.). 0.60N.N-dimethylcyclohexylamine 0.70 Water 0.75 Trichlorofluoromethane(Freon l 1 B) 18.00

Free Blown Panel Density 1.23 lbs./cu.ft.

Freezer Shrinkage 27.0%

Density 1.38 lbs./cu.ft.

Packing 12% Freezer Shrinkage 22.971

EXAMPLE 8 Component A Percent by Weight Nacconate 5050 (commercialtolylene diisocyanate containing a mixture of 2,4- and 2.6- isomers).

Component B 44.26 Percent by weight Freezer Shrinkage 17.492

EXAMPLE 8-Continued EXAMPLE 1 l-Continued Packed Panel [.41 lbs/cult.

Density Packing Freezer Shrinkage EXAMPLE 9 Component A Percent byWeight Nacconate 5050 (commercial tolylene diisocyanate containing amixture of 2,4- and 2,6- isomers). 44.26

Component B Percent by Weight Polyol of Example 1 25.00 Polyol ofExample 3 1.74 Polyol of Example 3 containing the addition of 2%phosphoric acid (86%) by weight,

based on the total weight of acid and polyol. 5.00 (l)-ethyleneoxide-(3)-propylene oxide ethylenediamine 3.95 Organo-siliconesurfactant L-5340 0.60 N,N-dimethy1cyclohexy1amine 0.70 Water 0.75Trichlorofluoromethane (Freon 118) 18.00

Free Blown Panel 1.30 pounds/cubic foot 10.1%

Density Freezer Shrinkage Packed Panel Density 1.41 pounds/cubic footPacking 8% Freezer Shrinkage 2.15%

EXAMPLE 10 Component A Percent by Weight Nacconate 5050 (commercialtolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers).

Component B 44.26 Percent by Weight Polyol of Example 1 18.40 Polyol ofExample 3 10.70 Polyoxypropy1ene(8)sorbitol 6.59 Organo-siliconesurfactant L-5340 (Union Carbide Co.). 0.60 N.N-dimcthylcyclohexylamine0.70 Water 0.75 Trichlorofluoromcthane (Freon 1 1B) 8.00

Free Blown Panel Density 1.23 lbs/cult.

38.2 Packed Panel Freezer Shrinkage Density 1.38 lbs/cult.

Packing 127! Freezer Shrinkage 24.30

EXAMPLE 1 1 Component A Percent by Weight Nacconate 5050 (commercialtolylene diisocyanate containing a mixture of 2.4- and 2.6- isomers).4426 Component B Percent by Weight Polyol of Example 1 18.4 Polyol ofExample 3 containing the addition of 1% phosphoric acid (86%) by weight.

based on the total weight of acid and polyol. 5.00 Polyol of Example 35.70 Polyoxypropylene(8)sorbitol 6.59

Organo-silicone surfactant 1.-5340 (Union Carbide Co.) 0.60N.N-dimethy1cyclohexy1amine 0.70 Water 0.75 Trichlorofluoromethane(Freon 1 13) 18.00

Free Blown Panel 1.28 pounds/cubic foot l 1.6% Packed Panel DensityFreezer Shrinkage Density 1.34 pounds/cubic foot Packing 5% FreezerShrinkage 5.8%

EXAMPLE 12 Component A Percent by Weight Nacconate 5050 (commercialtolylene diisocyanate containing a mixture of 2.4- and 2.6- isomers).44.26

Component B Percent by Weight Polyol of Example 1 18.40 Polyol ofExample 3 5.70 Polyol of Example 3 containing the addition of 2%phosphoric acid (86%) by weight.

based on the total weight of acid and polyol. 5.00Polyoxypropylene(8)sorbitol 6.54 Organo-silicone surfactant L-5340 0.60N,N-dimethylcyclohexylamine 0.70 Water 0.75 Trichlorofluoromethane(Freon 1 18) 18.00

Free Blown Panel 1.31 pounds/cubic foot 1.45%

Density Freezer Shrinkage Packed Panel Density 1.38 pounds/cubic footPacking 6% Freezer Shrinkage 1.43%

EXAMPLE 13 Component A Percent by Weight Nacconate 5050 (commercialtolylene diisocyanate containing a mixture of Coomponent A Percent byWeight Naceonate 5050 (commercial tolylene dnsoeyanate cuntammg amixture of 2.4- and lo isomers).

Component [3 Percent b Weight Polyol of Example 6 38.03 Phosphoric Acidl 0.10 ()rgann-silicone surfactant 1.5420 060 13 EXAMPLE l4-ContinuedN.N-dimethylcyclohexylamine 1.00 Water 0.75 Trichlorofluoromethane(Freon 1 1B) 1700 Free Blown Panel Density 1.37 lbs./cu.ft. FreezerShrinkage 10.1%

Packed Panel Density 1.51 1bs./cu.ft. Packing 10% Freezer ShrinkageEXAMPLE 15 Component A Percent by Weight Nacconate 5050 (Commercialtolylene diisocyanate containing a mixture of 2.4- and 2.6- isomers).

Component B 42.475 Percent by Weight The following Examples 16 to 21represent foams which were made by machine runs by the followingprocess. The polyols were blended in a -ga1lon container andthephosphoric acid. silicone surfactant, catalyst and water were added tothe polyol blend with stirring. The resulting blend was thoroughly mixedfor aboutv tenminutes at a temperature of about 72F. Chemical analysisof the resulting blend of polyols, phosphoric acid. surfactant,catalyst, and water confirm the formation of the desired phosphate saltsof the polyoxyalkylene amine based polyols utilized. Then thehalogenated hydrocarbon blowing agent was incorporated in the polyolblend. The above polyol blend is described hereinafter as the Bcomponent. Then the B component and A component (which is thepolyisocya- .nate) wereloaded into two tanks on an Admiral Urethane FoamMachine (manufactured by Admiral Equipment Corporation, Akron. Ohio).The temperature of each component was adjusted to 70F. and the correctratio'of A and B components was obtained by weighing a sample shot ofmaterial from the head or discharge opening in the foam machine withoutthe mixer in place. Then the mixer' was placed on the machine and foamwas made at 26.8 pounds per minute at mixer speed of 6.000 rpm. The foamwas poured into a 2 X 18 X 24 inch mold to free rise density. The top ofthe foam was then cut off level with the mold and the foam content ofthe mold weighed to determine the free rise density. For packed foams.approximately more of the mixture of the A and B components were addedto the mold than normally used: and a tight cover was placed over themold. Then the foam was allowed to rise to fill the confined volume ofthe mold to give a 10% -packed foam.

The percent freezer shrinkage of the products of the following Examples16 to 21 were determined by measuring the shrinkage of the moldedpolyurethane foam in the 18-inch direction after exposure of the foam to-2()F. temperatures for 16 hours. In Examples 16 to 21 the percent ofshrinkage considered acceptable within the bounds of the presentinvention for free blown foam panels and packed foam panels under theimmediately above-described testing procedure is the same as that statedabove in relation to the free blown foam panels and packed foam panelsof Examples 7 to 15.

EXAMPLE 16 Component A Parts by Weight Nacconate 5050 (commercialtolylcne diisocyanate containing a mixture of 2.4- and 2.6- isomers).44.26

Component B Parts by Weight Polyol of Example 1 18.40 Polyol of Example3 10.60 Phosphoric Acid (867: 0.10 Polyoxypropylene( 8 )-sorbitol 6.59Organo-silicone surfactant L-5340 (Union Carbide Co.). 0.60N.N-dimethylcyelohexylaminc 0.70 Water 0.75 Trichlorofluoromethane(Freon l l B) 17.00

Free Blown Panel Density 1.22 lbs./cu.ft. Freezer Shrinkage 12.5%

Packed Panel Density 1.33 lbs./cu.ft. Freezer Shrinkage 5.4%

EXAMPLE 17 Component A Parts by Weight Nacconate 5050 (commercialtolylene diisocyanatc containing a mixture of 2.4 and 2.6- isomers).

Component B 45 .73 Parts by Weight Component B Parts by Weight Polyol ofExample 1 18.94 Polyol of Example 3 10.75 Polyol of Example 6 6.77Phosphoric Acid (869? 0.25 Organo-silicone surfactant L-5 340 0.60N.N-dimethylcyelohexylamine 0.70 Water 0.75 Trich1orolluoromethane(Freon 118) 16.00

Free Blown Panel Density 1.3 pounds/cubic foot Freezer Shrinkage 15.5

Packed Panel Density 1.45 pounds/cubic foot Freezer Shrinkage 4.759;

EXAMPLE 19 Component A Parts by Weight Hylene TIC (commercial tolylenediisocyanate containing a mixture of 2.4- and 2,6- isomers).

Component B 45.24 Parts by Weight Free Blown Panel Nacconate 5050(commercial tolylene diisocyanate containing a mixture of 2,4- and 2.6-isomers).

Component B 44.82 Parts by Weight Polyol of Example 26.31 Polyol ofExample 2 11.27 Phosphoric Acid (86%) 0.25 Organo-silicone surfactantL-5340 0.60 N.N-dimethylcyclohexylamine 1.00 Water 0.75Trichlorofluoromethane (Freon 1113) 15.00

Free Blown Panel Density 1.32 pounds/cubic foot Freezer Shrinkage 4.5%

EXAMPLE 21 Component A Parts by Weight Naeeonate 5050 (commercialtolylene dnsocyanate containing a mixture of 2.4- and 2.6- isomers).45.01 I

omponent 13 Parts by Weight Polyol of Example 4 26.45 Polyol of Example2 l 1.3-1 Phosphoric Acid (867! 0.25 Organo-silicone surfactant L-53400.60 N.Ndimethylcyclohexylamine ater Trichlorotluoromethane (Freon 1 1B)15.00

l-ree Blown Panel Density 1.48 pounds/cubic foot Freezer Shrinkage 9.69}

Packed Panel Density 1.59 pounds/cubic foot Freezer Shrinkage Havingdescribed the invention. what is desired to be secured by Letters Patentis:

l. A polyol composition represented by the formulas:

wherein R" is selected from the group consisting of alkylene groupscontaining from 1 to 20 carbon atoms.

R is independently selected from the group consisting of alkylene groupscontaining from 1 to 6 carbon atoms. Q is independently selected fromthe group consisting ofhydrogen and (OR ).,H, R is independentlyselected from the group consisting of alkylene groups containing from 2to 6 carbon atoms. y is a number of from 1 to 20. is a number offrom 1to 20. 1 represents a number having an average value of 3 and m and pare independently selected values ofO or 1 with the proviso that atleast in or p is l. n has a value of from 0.03 to 0.5, t has a value of0.03 to 1.0 when the amine represented by formula (b) is a diamine and avalue of 0.05 to 1.5 and 0.05 to 2.0 when the amine represented byformula (b) is a triamine and tetramine, respectively.

2. A polyol composition of claim I comprised of a phosphate salt ofpolyoxyalkylene ethylenediamine containing an average of 4 to 20oxyalkylene groups per mol of ethylenediamine.

3. A polyol composition of claim 1 comprised of a phosphate salt ofpolyoxyethylene ethylenediamine containing an average of 4 to 8 ethyleneoxide groups per mol of ethylenediamine.

4. A polyol composition of claim 1 comprised of a phosphate salt ofpolyoxypropylene ethylenediamine containing an average of from 4 to 8propylene oxide groups per mol of ethylenediamine.

5. A polyol composition of claim 1 comprised of a phosphate salt ofpolyoxypropylene monoethanolamine containing an average of 3 to 8propylene oxide groups per mol of monoethanolamine.

6. A polyol composition of claim 1 comprised of a phosphate salt ofpolyoxypropylene diethylenctriamine containing an average of from 5 to 9propylene oxide groups per mol of diethylenetriamine.

7. A polyol composition of claim 1 comprised of a phosphate salt ofpolyoxypropylene triethanolamine containing an average of 3 to 8propylene oxide groups per mol of triethanolamine.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,890 ,389 DATED June 17, 1975 r vg o wf Raymond H. Fowler It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below: 0

Column 1, line 59 reads: "wwll" should read: -will.

Column 2, line 30 reads: "certain number" should read:

"certain number".

Column 2, line 34 reads: "certain number" should read:

-"certain number".

. Column 2 line 44, reads: "0.50" should read: 0 50%-.

Column 4, line 33 reads "functionality" should read:

--"functionality".

Column 8, line 32 reads: "Examples" should read: Example--.

Column 10, line 17 reads: "free blown foam panels" should read:

-"free blown foam panels"-.

. Column 10 line 19 reads: "packed foam panels" should read:

-=--"packed foam panels"-.

Column 10, line 21 reads: "free blown foam panels" should read:

---"free blown foam panels"-.

Column 10, line 22 reads: "packed foam panels" should read:

"packed foam panels".

Column 12, Example 13, after the line "2 ,4- and 2 ,6- isomer) pleaseinsert the line:

-Component B Percent by Weight-- Column 12, Example 14, line 61 reads:"Coomponent A should read: Component A--.

Column 14, lines 3 and 4 reads: "free blown foam panels and packed foampanels" should read: -"free blown foam panels" and "packedfoam panels"-.

Column 14, lines 6 and 7 reads: "free blown foam panels and packed foampanels" should read: -"free blown foam panels" and "packed foampanels"-.

Column 14, before Example 16, please insert the paragraph -In thefollowing Examples 16 to 21, all parts are by weight..

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3 890389 Page F 2 DATED 3 June 17, 1975 lNVENTOR(S Y Raymond H. Fowler it iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 16, Claim 1, line 7 reads:

I "H [H(OR' 1 -N-R"-1 'r- (OR' H1 H (H PO should read:

Signed and Scaled this twenty-eight D 3} Of October 1 9 75 [S AL] A ttest.

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Parentsand Trademarks

1. A POLYOL COMPOSITION REPRESENTED BY THE FORMULAS:
 2. A polyolcomposition of claim 1 comprised of a phosphate salt of polyoxyalkyleneethylenediamine containing an average of 4 to 20 oxyalkylene groups permol of ethylenediamine.
 3. A polyol composition of claim 1 comprised ofa phosphate salt of polyoxyethylene ethylenediamine containing anaverage of 4 to 8 ethylene oxide groups per mol of ethylenediamine.
 4. Apolyol composition of claim 1 comprised of a phosphate salt ofpolyoxypropylene ethylenediamine containing an average of from 4 to 8propylene oxide groups per mol of ethylenediamine.
 5. A polyolcomposition of claim 1 comprised of a phosphate salt of polyoxypropylenemonoethanolamine containing an average of 3 to 8 propylene oxide groupsper mol of monoethanolamine.
 6. A polyol composition of claim 1comprised of a phosphate salt of polyoxypropylene diethylenetriaminecontaining an average of from 5 to 9 propylene oxide groups per mol ofdiethylenetriamine.
 7. A polyol composition of claim 1 comprised of aphosphate salt of polyoxypropylene triethanolamine containing an averageof 3 to 8 propylene oxide groups per mol of triethanolamine.